1,2-Oxaphospholanes

ABSTRACT

2-Oxo-2-alkoxy-5-dialkylphosphono-1,2-oxaphospholanes of the formula ##STR1## in which R 1  to R 7  are hydrocarbon radicals can be prepared from α,β-unsaturated ketones and 2 or more moles of a dialkyl phosphite. Obviously α-ketophosphonates are intermediates of this reaction, as these compounds react with 1 or more moles of dialkyl phosphite in yielding the oxaphospholanes too. Both reactions are promoted by alkaline catalysts. 
     The new oxaphospholane derivatives are considerably stable against thermal decomposition. They are compatible with polymeric materials and can be used as flame protecting agent for plastics and resins, for example, in polyurethane foams.

This application is a continuation-in-part of copending application Ser.No. 499,888, filed Aug. 23, 1974, now abandoned.

This invention pertains to new 1,2-oxaphospholane-5-phosphonic acidesters, a process for their manufacture, a method of using them asflameproofing agents for thermoplastic polymers, polyurethanes,cellulose and cellulose derivatives and also the substrates protected bythem.

The new compounds have the general formula I ##STR2## wherein each ofR₁, R₂ and R₃ independently represents a monovalent aliphatic,cycloaliphatic or araliphatic radical or a tetrahydrofurfuryl radical,each of R₄, R₅ and R₆ independently represents hydrogen, alkyl or amonovalent aromatic or heteroaromatic radical, and R₇ represents alkylor a monovalent aromatic or heteroaromatic radical.

A monovalent aliphatic radical represented by R₁, R₂ or R₃ can be alinear or branched alkyl or alkenyl radical which is unsubstituted orsubstituted by halogen or alkoxy groups.

Examples of R₁, R₂ or R₃ when alkyl of 1 to 18 carbon atoms are methyl,ethyl, isopropyl, n-butyl, 2-ethylhexyl, isooctyl, n-dodecyl andn-octadecyl.

Examples of R₁, R₂ or R₃ when alkenyl of 3 to 18 carbon atoms are allyl,methallyl and oleyl.

When R₁, R₂ or R₃ is haloalkyl of 2 to 18 carbon atoms, such groups are2-chloroethyl, 2-bromoethyl and 2,3-dibromopropyl.

When R₁, R₂ or R₃ is alkoxyalkyl of not over 18 carbon atoms, suchgroups include 2-ethoxyethyl, 2-methoxyethyl, 2-n-butoxyethyl and2-methoxypropyl.

Where R₁, R₂ or R₃ represent a monovalent cycloaliphatic radical, suchgroups are cycloalkyl of 5 to 8 carbon atoms such as cyclopentyl,cyclohexyl and cyclooctyl.

When R₁, R₂ or R₃ represent a monovalent araliphatic radical, examplesare aralkyl of 7 to 15 carbon atoms or aralkyl of 7 to 15 carbon atomssubstituted by halogen or alkoxy groups of 1 to 4 carbon atoms such asbenzyl, 2-methylbenzyl, α,α-dimethylbenzyl, β-phenylethyl,4-chlorobenzyl or 4-methoxybenzyl.

Alkyl radicals represented by R₄, R₅, R₆, or R₇ can be linear orbranched alkyl radicals, e.g., methyl, ethyl, isopropyl, tert-butyl,n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-dodecyl or n-octadecyl. Anaromatic radical represented by these same substituents can be phenyl,naphthyl or diphenylyl radical which is unsubstituted or which issubstituted by halogen, alkyl and/or alkoxy groups. A monovalentheteroaromatic radical represented by these same substituents can beheteroaromatic radical which is unsubstituted or which is substituted byhalogen, alkyl, phenyl and/or alkoxy groups, e.g., correspondingradicals of furan, thiophene, cumarone, dibenzofuran, pyridine,quinoline or carbazole.

Preferred compounds are those of the formula I wherein each of R₁, R₂and R₃ independently represents alkyl with 1 to 18 carbon atoms,haloalkyl or alkoxyalkyl having not more than 18 carbon atoms, alkenylwith 3 to 18 carbon atoms, tetrahydrofurfuryl, cycloalkyl with 5 to 8carbon atoms, aralkyl with 7 to 15 carbon atoms or aralkyl withaltogether 7 to 15 carbon atoms which is substituted by halogen and/oralkoxy groups of 1 to 4 carbon atoms, R₄ represents hydrogen or methyl,R₅ represents hydrogen, alkyl with 1 to 8 carbon atoms, aryl with 6 to10 carbon atoms, aryl with 6 to 10 carbon atoms which is substituted byhalogen, alkyl or alkoxy groups with 1 to 4 carbon atoms, or representsfuryl, thienyl or pyridyl, R₆ represents hydrogen, methyl or phenyl, andR₇ represents alkyl with 1 to 8 carbon atoms, aryl with 6 to 10 carbonatoms, aryl with 6 to 10 carbon atoms which is substituted by halogen,alkyl or alkoxy groups with 1 to 8 carbon atoms, or represents furyl,thienyl or pyridyl. By halogen is meant in this context fluorine,chlorine or bromine.

Other preferred compounds have the formula Ia ##STR3## wherein each ofR_(a), R_(b) and R_(c) independently represents alkyl of 1 to 18 carbonatoms, haloalkyl with 2 to 18 carbon atoms, alkoxyalkyl having not morethan 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl withto 8 carbon atoms, aralkyl with 7 to 15 carbon atoms, aralkyl withaltogether 7 to 15 carbon atoms which is substituted by halogen oralkoxy groups of 1 to 4 carbon atoms, or is tetrahydrofurfuryl,

R_(d) represents hydrogen or methyl,

R_(e) represents hydrogen, alkyl with 1 to 8 carbon atoms, aryl with 6to 10 carbon atoms, aryl with 6 to 10 carbon atoms which is substitutedby halogen, alkyl or alkoxy groups with 1 to 4 carbon atoms, or furyl,thienyl or pyridyl, and with the proviso that when R_(e) is hydrogen oralkyl, none of R_(a), R_(b) or R_(c) can be alkyl,

R_(f) represents hydrogen, methyl or phenyl, and

R_(g) represents alkyl with 1 to 8 carbon atoms, aryl with 6 to 10carbon atoms, aryl with 6 to 10 carbon atoms which is substituted byhalogen, alkyl or alkoxy with 1 to 8 carbon atoms, or is furyl, thienylor pyridyl.

By halogen is meant in this context fluorine, chlorine or bromine.

Compounds of the formula I which constitute a specially preferred classof these compounds are those wherein each of R₁ and R₂ independentlyrepresents a monovalent aliphatic, cycloaliphatic or araliphaticradical, R₃ is the same as either R₁ or R₂, each of R₄, R₅ and R₆independently represents hydrogen, alkyl or a monovalent aromatic orheteroaromatic radical, and R₇ represents alkyl or a monovalent aromaticor heteroaromatic radical.

To this class of compounds belong the compounds of the formula I whereineach R₁ and R₂ independently represents alkyl with 1 to 18 carbon atoms,haloalkyl or alkoxyalkyl having not more than 18 carbon atoms, alkenylwith 3 to 18 carbon atoms, tetrahydrofurfuryl, cycloalkyl with 5 to 8carbon atoms, aralkyl with 7 to 15 carbon atoms or aralkyl withaltogether 7 to 15 carbon atoms which is substituted by halogen and/oralkoxy groups of 1 to 4 carbon atoms, R₃ is the same as either R₁ or R₂,R₄ represents hydrogen or methyl, R₅ represents hydrogen, alkyl with 1to 8 carbon atoms, aryl with 6 to 10 carbon atoms, aryl with 6 to 10carbon atoms which is substituted by halogen, alkyl or alkoxy groups of1 to 4 carbon atoms, or represents furyl, thienyl or pyridyl, R₆represents hydrogen, methyl or phenyl, and R₇ represents alkyl with 1 to8 carbon atoms, aryl with 6 to 10 carbon atoms, aryl with 6 to 10 carbonatoms which is substituted by halogen, alkyl or alkoxy groups with 1 to8 carbon atoms, or represents furyl, thienyl or pyridyl.

Other specially preferred compounds are those of formula Ia wherein eachof R_(a) and R_(b) independently denotes alkyl of 1 to 18 carbon atoms,haloalkyl of 2 to 18 carbon atoms, alkoxyalkyl having not more than 18carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8carbon atoms, aralkyl with 7 to 15 carbon atoms or aralkyl withaltogether 7 to 15 carbon atoms which is substituted by halogen oralkoxy groups of 1 to 4 carbon atoms, or is tetrahydrofurfuryl; R_(c) isthe same as either R_(a) or R_(b) ; R_(d) represents hydrogen or methyl;R_(e) represents hydrogen, alkyl with 1 to 8 carbon atoms, aryl with 6to 10 carbon atoms, aryl with 6 to 10 carbon atoms which is substitutedby halogen, alkyl or alkoxy of 1 to 4 carbon atoms, or is furyl, thienylor pyridyl, and with the proviso that when R_(e) is hydrogen or alkyl,none of R_(a), R_(b) or R_(c) can be alkyl; R_(f) represents hydrogen,methyl or phenyl; and R_(g) represents alkyl with 1 to 8 carbon atoms,aryl with 6 to 10 carbon atoms, aryl with 6 to 10 carbon atoms which issubstituted by halogen, alkyl or alkoxy with 1 to 8 carbon atoms, or isfuryl, thienyl or pyridyl.

By halogen is meant also in this context chlorine or bromine.

Particularly preferred compounds of the formula I are those wherein R₁,R₂ and R₃ are identical and represent linear or branched alkyl radicalwith 1 to 8 carbon atoms, alkoxyalkyl with 3 to 6 carbon atoms,2-chloroethyl, 2-bromoethyl, alkenyl with 3 to 4 carbon atoms,cyclohexyl, benzyl or tetrahydrofurfuryl, R₄ represents hydrogen ormethyl, R₅ represents hydrogen, methyl, ethyl, phenyl, naphthyl; phenylor naphthyl substituted with 1 to 5 chlorine or bromine atoms; p-tolyl,xylyl, p-anisyl, 2-furyl, 2-thienyl or pyridyl, R₆ represents hydrogenor methyl, and R₇ represents methyl, ethyl, phenyl, phenyl substitutedwith 1 to 5 chlorine or bromine atoms; p-tolyl, xylyl, p-anisyl, 2-furylor 2-thienyl.

Other particularly preferred compounds of formula Ia are those whereinR_(a), R_(b) and R_(c) are identical and represent alkyl of 1 to 8carbon atoms, alkoxyalkyl with 3 to 6 carbon atoms, alkoxyalkyl with 3to 6 carbon atoms, 2-chloroethyl, 2-bromoethyl, alkenyl with 3 to 4carbon atoms cyclohexyl, benzyl or tetrahydrofurfuryl; R_(d) representshydrogen or methyl; R_(e) represents hydrogen, methyl, ethyl, phenyl,naphthyl; phenyl or naphthyl substituted by 1 to 5 chlorine or bromineatoms; p-tolyl, p-anisyl, xylyl, 2-furyl, 2-thienyl or 2-pyridyl, andwith the proviso that when R_(e) is hydrogen, methyl or ethyl, R_(a),R_(b) and R_(c) cannot be alkyl; R_(f) represents hydrogen or methyl;and R_(g) represents methyl, ethyl, phenyl, phenyl substituted with 1 to5 chlorine or bromine atoms, p-tolyl, xylyl, p-anisyl, 2-furyl or2-thienyl.

The surprising discovery has been made that it is possible tomanufacture the compounds of the formula Ia, in which R_(c) is the sameas R_(a) or R_(b), by a novel process which comprises reacting anα,β-unsaturated ketone of the formula II ##STR4## with at least 2 molesof a phosphite of the formula III ##STR5## in the presence of a base,with or without the addition of a solvent.

Examples of α,β-unsaturated ketones of the formula II are methyl vinylketone, ethyl vinyl ketone, phenyl vinyl ketone, mesityl oxide, methylisopropenyl ketone, benzalacetone, benzalacetophenone or4-chlorobenzalacetone. Such ketones can be manufactured by knownmethods, for example, by condensation of the appropriate methyl ketoneswith aldehydes or ketones. Other α,β-unsaturated ketones useful in thisinvention include α-ionone, β-ionone, 4-methoxy-3-buten-2-one,3-penten-2-one, isophorone and phorone.

The phosphites of the formula III are known compounds of industrialavailability. Examples thereof are dialkyl phosphites, e.g., dimethyl,diethyl or dioctyl phosphite, dicycloalkyl phosphites, e.g.,dicyclohexyl phosphite, diaralkyl phosphites, e.g., dibenzyl phosphite,and mixed phosphites, e.g., methyl butyl phosphite, methyl benzylphosphite or isopropyl cyclohexyl phosphite.

In the reaction there are used 2 moles, preferably 2.5 to 3.5 moles, ofa compound of the formula III for each mole of the compound of theformula II.

Examples of bases which catalyze the reaction are principally alkalimetals, alkali metals or alkaline earth metal alkoxides, alkali metalamides and hydrides. Particularly effective are the metals sodium andpotassium, sodium ethoxide, sodium methoxide, potassium tert-butoxide,lithium amide and calcium hydride; but the two metals, sodium andpotassium, are particularly suitable for the purpose. Normally,catalytic amounts of these bases suffice to initiate the reaction. It issometimes advantageous to add further amounts of base during thereaction.

If the process according to the invention is carried out with theaddition of a solvent, then suitable solvents are primarilyhydrocarbons, e.g., benzene, toluene, xylene, ligroin, hexane orheptane, also alcohols, e.g., methanol, ethanol or isopropanol, orethers, e.g., diethyl ether, dioxane or tetrahydrofuran.

The reaction can be carried out by dissolving the ketone of the formulaII and adding dropwise a portion of the phosphite of the formula III andthe base. Upon onset of the reaction, the remainder of the phosphiteand, if necessary, further amounts of base are added by gradual amounts.It is also possible to premix the phosphite with the catalyst and to addthe ketone of the formula II dropwise.

In another embodiment, the compounds of the formulas II and III andoptionally the solvent are first mixed and then the base, which can alsobe dissolved in the solvent, is added to this mixture and the reactionis brought to completion by heating.

The oxaphospholanes of the formula Ia are isolated by customary methods,for example, by distillation. Desirably the base is neutralized beforethe isolation by an equivalent amount of an acid, for example, aceticacid.

The reaction of dialkyl phosphites with α,β-unsaturated ketones hasalready been thoroughly investigated by various experts. It has hithertobeen considered the rule that in the reaction only 1 mole of phosphiteis added to the double bond forming the γ-ketophosphonates (seeHouben-Weyl, Methoden der Organischen Chemie, vol. 12/1, pages 465-467,G. Thieme Verlag, Stuttgart, 1963). If diphosphonates were alsoobtained, these occurred in moderate yield in addition to themonophosphonates (A. N. Pudovik, Zhurnal Obshch. Khim., 22, 1371,(1952); Chem. Abstr. 47, 4837, (1953). It was therefore surprising thatin the process described herein 2 moles of phosphite are added easily.It was furthermore surprising that the γ-phosphono-α-hydroxyphosphonatesevidently formed as intermediate cyclize under the reaction conditionsrapidly and virtually completely to give the1,2-oxaphospholane-5-phosphonates.

The reaction of 1 mole of acetylactone, α,β-diketone, with 2 moles ofdiethyl phosphite was reported by B. A. Arbuzov et al, Izv. Akad. Nauk.SSSR, Ser Khim 12, 2757 (1971) to give2-oxo-2-ethoxy-3-hydroxy-3,5-dimethyl-5-diethylphosphono-1,2-oxaphospholane.This compound, although somewhat related to the compounds of thisinvention, possesses quite different chemical properties due to thepresence of the 3-hydroxy group, and can undergo a variety of chemicalreactions unavailable for the instant compounds.

It has furthermore been found that oxaphospholane derivatives of theformula I can also be manufactured from the known γ-ketophosphonates byaddition of dialkyl phosphites. This is an indication that the reactiondiscussed above probably proceeds via the stage of theγ-ketophosphonates. It is therefore possible to carry out the reactionin two partial steps, the first being the known addition of 1 mole ofphosphite to α,β-unsaturated ketones to form the γ-ketophosphonates andthe second being the reaction with a second mole of phosphite to formthe oxaphospholanes. This second step is just as surprising and novel asthe single step main process.

The invention therefore also provides a process for the manufacture ofcompounds of the formula Ia, which comprises reacting a compound of theformula IV ##STR6## with at least one mole of a phosphite of the formulaIII in the presence of a base, with or without the addition of asolvent. In the formula IV, the substituents R_(c) to R_(g) have thesame meanings assigned to them as in respect of the compounds of theformula Ia. The catalysts and solvents suitable for use in this processare the same as those for the single step main process describedhereinbefore, and the reaction and isolation of the products are carriedout in the same way.

This modification is principally of importance for the manufacture ofthose compounds of the formula Ia in which R_(c) is different from R_(a)and R_(b).

Examples of individual compounds of formula I are the following1,2-oxaphospholane derivatives:

2-oxo-2-methoxy-5-ethyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-ethoxy-5-ethyl-5-diethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-5-methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-ethoxy-5-methyl-5-diethylphosphono-1,2-oxaphospholane

2-oxo-2-isopropoxy-5-methyl-5-diisopropylphosphono-1,2-oxaphospholane.

2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane

2-oxo-2-isopropoxy-3,3,5-trimethyl-5-diisopropylphosphono-1,2-oxaphospholane

2-oxo-2-butoxy-3,3,5-trimethyl-5-dibutylphosphono-1,2-oxaphospholane

2-oxo-2-(2-ethylhexyloxy)-3,3,5-trimethyl-5-bis-(2-ethylhexyl)-phosphono-1,2-oxaphospholane

2-oxo-2-butoxy-5-methyl-5-dibutylphosphono-1,2-oxaphospholane

2-oxo-2-octoxy-5-methyl-5-dioctylphosphono-1,2-oxaphospholane

2-oxo-2-(2-ethylhexyloxy)-5-methyl-5-bis-(2-ethylhexyl)phosphono-1,2-oxaphospholane

2-oxo-2-octadecyloxy-5-methyl-5-dioctadecylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3,5-dimethyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-ethoxy-3,5-dimethyl-5-diethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3,4-diemthyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-ethoxy-3,4-diemthyl-5-diethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-(2-chloroethyloxy)-5-methyl-5-bis-(2-chloroethyl)phosphono-1,2-oxaphospholane

2-oxo-2-(2-methoxyethyloxy)-5-methyl-5-bis-(2-methoxyethyl)phosphono-1,2-oxaphospholane

2-oxo-2-benzyloxy-5-methyl-5-dibenzylphosphono-1,2-oxaphospholane

2-oxo-2-(4-chlorobenzyloxy)-5-methyl-5-bis-(4-chlorobenzyl)phosphono-1,2-oxaphospholane

2-oxo-2-(4-bromobenzyloxy)-5-methyl-5-bis-(4-bromobenzyl)phosphono-1,2-oxaphospholane

2-oxo-2-methoxy-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-ethoxy-5-phenyl-5-diethylphosphono-1,2-oxaphospholane

2-oxo-2-(2-chloroethoxy)-3,3,5-trimethyl-5-bis-(2-chloroethyl)phosphono-1,2-oxaphospholane

2-oxo-2-benzyloxy-3,3,5-trimethyl-5-dibenzylphosphono-1,2-oxaphospholane

2-oxo-2-cyclohexyloxy-3,3,5-trimethyl-5-dicyclohexylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-phenyl-5-methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-ethoxy-3-phenyl-5-methyl-5-diethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(4-chlorophenyl)-5methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(4-bromophenyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(4-methylbenzyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(4-methoxyphenyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(furyl-2)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(thienyl-2)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methyoxy-3-(pyridyl-2)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-methyl-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-methyl-5-(4-chlorophenyl)-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3,5-diphenyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-ethoxy-3,5-diphenyl-5-diethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(4-chlorophenyl)-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3,5-bis-(4-chlorophenyl)-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-phenyl-5-(4-chlorophenyl)-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(4-methylphenyl)-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-(4-methoxyphenyl)-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3-phenyl-5-(4-methylphenyl)-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-methoxy-3,5-diphenyl-5-dimethylphosphono-1,2-oxaphospholane

2-oxo-2-allyloxy-3,3,5-trimethyl-5-diallylphosphono-1,2-oxaphospholane

2-oxo-2-tetrahydrofurfuryl-3,3,5-trimethyl-5-di-(tetrahydrofurfuryl)phosphono-1,2-oxaphospholane

The compounds of the formula I are outstanding flameproofing agents forthermoplastic polymers, polyurethanes, cellulose and also for cellusosederivatives. It has long been known that phosphorus-containing compoundscan be used as flameproofing agents for polymers, but it is normallynecessary to use the phosphorus compounds in high concentrations, whichresults as a rule in some deterioration of the physical properties ofthe polymers.

The surprising discovery has now been made that the new1,2-oxaphospholane of the formula I impart an adequate flame resistanceto the polymers even in relatively low concentrations. Moreover, onaccount of their considerable heat stability, they have only a minuteinfluence on the physical properties of the substrates. Further, theyare also usable in reactive systems, such as in polyurethane foams,which both in their manufacture and use, are highly sensitive towardsadditives.

Examples of thermoplatic polymers which can be flame-protected with thecompounds of the formula I are:

1. Polymers which are derived from singly or doubly unsaturatedhydrocarbons, such as polyolefins, e.g., polyethylene, polypropylene,polyisobutylene, polymethylbutene-1, polymethylpentene-1, polybutene-1,polyisoprene, polybutadiene, polystyrene, polyisobutylene, copolymers ofthe monomers from which the cited homopolymers are derived, such asethylene-propylene copolymers, propylene-butene-1 copolymers,propylene-isobutylene copolymers, styrene-butadiene copolymers, andterpolymers of ethylene and propylene with a diene, e.g., hexadiene,dicyclopentadiene or ethyldene norbornene; mixtures of the abovementioned homopolymers, e.g., mixtures of polypropylene andpolyethylene, polypropylene and polybutene-1, polypropylene andpolyisobutylene.

2. Halogen-containing vinyl polymers, e.g., polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, but also polychloropreneand chlorinated rubbers.

3. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, e.g., polyacrylates and polymethacrylates, polyacrylamides andpolyacrylonitrile and copolymers thereof with other vinyl compounds,such as acrylonitrile/butadine/styrene, acrylonitrile/styrene andacrylonitrile/styrene/acrylic ester copolymers.

4.Polymers which are derived from unsaturated alcohols and amines andtheir acyl derivatives or acetals, such as polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, and copolymers thereof with other vinyl compounds,e.g., ethylene/vinyl acetate copolymers.

5. Polyacetals, e.g., polyoxymethylene and polyoxyethylene, and alsothose polyoxymethylenes that contain ethylene oxide as comonomer.

6. Polyphenylene oxides.

7 Polycarbonates.

8. Polysulfones.

9. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or aminocarboxylic acids or from thecorresponding lactams, e.g., polyamide 6, polyamide 6/6, polyamide 6/10,polyamide 11, and polyamide 12.

10. Polyesters which are derived from dicarboxylic acids and dialcoholsand/or the corresponding lactones, e.g., polyethylene terephthalate,polybutylene terephthalate, polycyclohexane-1,4-dimethyleneterephthalate.

The flameproofing of cellulose and cellulose derivatives is possible inthose cases where the polymer is processed from solution or from themelt, so that the flameproofing agent can be added to this solution ormelt. The cellulose xanthogenate solutions which are known as viscosesolutions and which are used for the manufacture of fibers and sheets ofregenerated cellulose are one example. Solutions of cellulose acetate inorganic solvents are another example. Polyurethanes which can beflameproofed with the compounds of the formula I can be both linear andbranched polyurethanes such as are used for the manufacture of films,fibers, brushes, coatings, elastic materials and rigid and soft foamplastics. The flameproofing of polyurethane foam plastics is ofparticular importance since such foams, like all materials having alarge surface area, burn more easily than compact materials.

It is common knowledge that such polyurethane foams or coatingcompositions are manufactured from polyhydroxy compounds, e.g.,polyester or polyethers which contain hydroxy groups on the one hand andpolyisocyanates, e.g., toluene diisocyanate, on the other. Theintroduction of flameproofing agents of the formula I can beaccomplished by adding them to the starting components mentionedhereinbefore, i.e., simultaneously with the manufacture of thepolyurethanes, since the oxaphospholane derivatives scarcely influencethe pot life and curing time. Noninflammable polyurethane foam plasticsor coatings with excellent mechanical properties and very goodresistance to aging are thereby obtained.

The compounds of the formula I are normally added to the citedsubstrates in an amount of 2 to 30% by weight, preferably 2to 20% byweight, based on the substrate. The addition can be carried out beforeor during the manufacture of the substrate by polymerization; butfrequently the compounds are added to the finished polymers before orduring their processing.

In addition to the flameproofing agents of formula I, it is alsopossible to add to the polymeric substrates other flameproofing agents,e.g., organic halogen compounds, antimony oxide or other phosphoruscompounds. It is furthermore possible to add other customary and knownadditives, e.g., antioxidants, heat stabilizers, UV absorbers,fluorescent brighteners, antistatic agents, lubricants, softeners,emulsifiers, pigments, carbon black, asbestos, kaolin, talcum, glassfibers or other fillers and reinforcing agents.

The manufacture and utility of the oxaphospholanes of the formula I areillustrated in more detail in the following examples:

EXAMPLE 12-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane

10 ml of diethyl phosphite was added to a solution of 98.1 g (1 mole) ofmesityl oxide in 300 ml of benzene, and the mixture was then heated to80° C. About 200 mg of metallic sodium was added to the almost boilingsolution, whereupon an exothermic reaction commenced. The reaction wasbrought to completion over the course of 10 minutes by gradual additionof altogether 345.0 g (2.5 moles) of diethyl phosphite and 4.2 g ofsodium. The reaction mixture was stirred for an additional 10 minutes,neutralized with 11 g of glacial acetic and evaporated in vacuum. Theresidue was distilled in high vacuum. The main fraction distilled as analmost colorless oil at 136°-139° C. and 0.035 mm Hg. Analysis bynuclear magnetic resonance and mass spectrum showed this fraction to be2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane ofthe empirical formula C₁₂ H₂₆ O₆ P₂ (MW = 328.29).

Analysis:

Calc: C 43.90; H 7.99; P 18.92.

Found: C 44.30; H 8.00; P 18.0.

The yield was 45.3% of theory.

The same reaction was carried out with 392 g (4 moles) of mesityl oxideand 1,660 g (12 moles) of diethyl phosphite in 1,200 ml of benzene andin the presence of 9.5 g of sodium. Upon completion of the reaction (40minutes), the reaction mixture was neutralized with 24.8 g of glacialacetic acid and distilled to yield 995.7 g of2-oxo-2-ethoxy-3,3,5m-trimethyl-5-diethylphosphono-1,2-oxaphospholane at136°-140° C. at 0.02-0.04 Torr. This corresponded to a yield of 75.9% oftheory.

EXAMPLE 22-Oxo-2-methoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane

A solution of 30.0 g of sodium methoxide in 90 ml of methanol was addeddropwise to a mixture of 220 g of dimethyl phosphite and 98 g of mesityloxide over the course of 2 hours in such a way that the reactiontemperature did not exceed 65° C. The clear solution was subsequentlyheated for 2 hours to 70° C. The reaction mixture was concentrated invacuo and the residue was taken up in 200 ml of toluene. The solutionwas filtered and the filtrate distilled. The2-oxo-2-methoxy-3,3,5-trimethyl-5-dimethylphosphone-1,2-oxaphospholanedistilled at 158°-160° C. at 0.6 mm Hg in the form of a colorless,viscous oil.

Analysis for C₉ H₂₀ O₆ P₂ (MW = 286.20): Calc: C 37.80; H 7.05; P 21.65.Found: C 37.79; H 7.04; P 21.32.

EXAMPLE 32-Oxo-2-tetrahydrofurfuryloxy-3,3,5-trimethyl-5-bis(tetrahydrofurfuryl)phosphone-1,2-oxaphospholane

As described in Example 1, a mixture of 37.6 g ofbis-(tetrahydrofurfuryl) phosphite and 4.9 g of mesityl oxide in 80 mlof benzene was reacted by heating in the presence of 1.3 g of sodiumover the course of 1 hour. The reaction was vigorously exothermic. Thesodium was neutralized by addition of 3.4 g of glacial acetic acid. Theinorganic salt was extracted from the mixture with 2 portions of 20 mlof water. The benzene solvent was removed in a rotary evaporator,leaving as residue 32.6 g of crude product which still containeddi-tetrahydrofurfuryl phosphite. Distillation of 4.3 g of the crudeproduct in a bulb tube oven in high vacuum yielded the desired productat an oven temperature between 185° C. and 230° C. and a pressure of0.01 mm Hg.

Yield: 2.07 grams

Analysis, C₂₁ H₃₈ O₉ P₂ (MW = 496.48): Calc: C 50.8; H 7.7; P 12.5.Found: C 49.5; H 7.7; P 12.6.

Although the mass spectrum did not show the molecular peak at ^(m) /e496, it did show instead the M+H peak at ^(m) /e 497. Fragmentscharacteristic of this compound occurred at ^(m) /e 426 (M^(+--C) ₄ H₆O) and 413 (M^(+--C) ₅ H₇ O).

EXAMPLE 4

2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane

98 g of mesityl oxide (1.0 mole) and 415 g of diethyl phosphite (3.0moles) were dissolved in 300 ml of benzene. 200 ml of this solution washeated to the boiling point. A catalytic amount of sodium was addedwhereupon a vigorous exothermic reaction commenced, and the mixtureboiled by itself after removal of the heating bath. After the sodiumdissolved, the reaction came practically to a stop and was initiatedagain by addition of a further amount of sodium. In this manner sodiumwas added until the main reaction was over. Then about one third of theremaining solution was added, and this was also reacted as previously byadding sodium. The remaining two thirds of the solution were thenreacted in the same way. Altogether 3.0 g of sodium was used over thecourse of 25 minutes. The entire reaction mixture was allowed tocontinue to react for 15 minutes at reflux. It was then neutralized with8 g of glacial acetic acid and diluted with 350 ml of benzene. After thereaction solution cooled, it was washed with two portions of water of 75and 20 ml respectively. The combined aqueous phases were extracted with50 ml of benzene twice to give a solution in benzene which was combinedwith the chief portion, dried with Na₂ SO₄ and concentrated in a rotaryevaporator. Distillation yielded 118.5 g of a first fraction of b.p.46°-68° C./8 mm Hg, which largely consisted of diethyl phosphite, and280.8 g (85.6% of theory) of the oxophospholane which boiled at122°-132° C. at 0.008 mm Hg. Gas chromatography showed the product to beabout 95% pure. 8.2 g remained as the distillation residue.

EXAMPLE 52-Oxo-2-isopropoxy-3,3,5-trimethyl-5-diisopropylphosphone-1,2-oxaphospholane

As described in Example 4, a mixture of 19.6 g of mesityl oxide (0.20mole), 99.6 g of diisopropyl phosphite (0.60 mole) and 100 ml of benzenewas reacted with 2.1 g of sodium as catalyst over the course of 10minutes. The reaction was vigorously exothermic. After a subsequentreaction for 15 minutes at the boiling temperature, the reaction mixturewas neutralized with 5.5 g of glacial acetic acid and diluted with 150ml of benzene. After the reaction solution cooled, it was extracted with20 ml of benzene twice, and the extract was combined with the chiefportion, dried over Na₂ SO₄ and concentrated in a rotary evaporator. Thedistillation yielded 27.5 g of a first fraction with a boiling point of68°-75° C./10 mm Hg and consisting of virtually pure diisopropylphosphite as well as 58.0 g (78.3%) of the oxaphospholane which boiledat 120°/0.02 mm Hg to 125°C./0.05 mm Hg; 5.3 g remained as residue.

Analysis, for C₁₅ H₃₂ O₆ P₂ (MW = 370.37): Calc: C 48.64; H 8.71; P16.73. Found: C 48.77; H 8.92; P 16.37.

The mass spectrum showed the molecular peak at ^(m) /e 370.

EXAMPLE 62-Oxo-2-ethoxy-4,5-dimethyl-5-diethlphosphono-1,2-oxaphospholane

In analogous manner to Example 4, a mixture of 25 g of freshly distilledmethyl isopropenyl ketone (0.30 mole), 124 g of diethyl phosphite (0.90mole) and 75 ml of benzene was reacted with 2.5 g of sodium over thecourse of 10 minutes. The reaction was vigorously exothermic. After asubsequent reaction for 10 minutes at the boiling temperature, thereaction mixture was neutralized with glacial acetic acid and dilutedwith 300 ml of benzene. After the reaction solution cooled, it wasextraced with 60 ml of H₂ O. The aqueous phase was extracted twice with60 and 30 ml of benzene respectively, and the extract was combined withthe chief portion, dried over Na₂ SO₄ and concentrated in a rotaryevaporator. Distillation yielded 49.2 g (52.2% of theory) of theoxaphospholane of b.p. 128°-132° C./0.002 mm Hg.

Analysis, for C₁₁ H₂₄ O₆ P₂ (MW = 314.26). Calc: C 42.04; H 7.70; P19.71. Found: C 41.78; H 7.69; P 19.39.

The mass spectrum showed the molecular peak at ^(m) /e 314.

EXAMPLE 72-Oxo-2-butoxy-3,3,5-trimethyl-5-dibutylphosphono-1,2-oxaphospholane

A reaction solution was prepared from 194 g (1 mole) of freshlydistilled dibutyl phosphite and 32.4 g (0.33 mole) of mesityl oxide in200 ml of absolute benzene. 30 ml of this mixture was put into thereaction flask and treated with about 50 mg of sodium. An exothermicreaction commenced and the temperature rose to 70° C. After the reactionsubsided, the mixture was brought to reflux temperature by addition tothe reaction solution in small amounts of 1.5 g sodium. Stirring wascontinued for 1 hour at 70° C. and the reaction mixture was subsequentlyneutralized with glacial acetic acid. Distillation yielded the productwith a boiling point of 158°-162° C./0.01 mm.

EXAMPLE 82Oxo-2-cyclohexoxy-3,3,5-trimethyl-5-dicyclohexylphosphono-1,2-oxaphospholane

88 g (0.35 mole) of freshly distilled dicyclohexyl phosphite wasdissolved in 150 ml of absolute benzene, and the solution was warmed to50° C. After addition of 2 g of sodium, 15 g (0.14 mole) of freshlydistilled mesityl oxide was added dropwise. The exothermic reactioncaused the temperature of the mixture to rise to 70° C. Aftertermination of the reaction, the reaction mixture was stirred forfurther 2 hours and then neutralized with glacial acetic acid. Thefiltered solution was distilled, and the product with a boiling point of150°-153° C./0.01 mm Hg was obtained.

EXAMPLE 92-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane

690 g of diethyl phosphite and 50 g of a sodium ethoxide solution (17 gof sodium dissolved in 83 g of ethanol) were mixed and with stirring,245.5 g of mesityl oxide was dropped into this solution over the courseof 40 minutes. During the dropwise addition an exothermic reaction tookplace, the reaction temperature rising from 20° to 101° C. when up tohalf the amount of mesityl oxide was added. The temperature then fell to75° C. when the second half of the mesityl oxide was added. Thecolorless, clear solution was stirred for 50 minutes and the temperaturein the reaction mixture fell to 39° C. Then an additional 25 g of sodiumethoxide solution was added all at once, whereupon the temperature ofthe reaction mixture rose from 39° to 84° C. The reaction mixture wasstirred for 30 minutes and then 25 g of sodium ethoxide solution wasadded. The resultant reaction mixture was stirred for 3 hours at roomtemperature and subsequently neutralized with 15 g of glacial aceticacid. Distillation of this reaction mixture yielded at 162°-167° C./0.5mm 626 g of2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane asa colorless liquid. Chromatographic analysis showed a purity of 99.1%.

EXAMPLE 10 2-Oxo-2-ethoxy-5-methyl-5-diethylphosphono-1,2-oxaphospholane

276 g (2 moles) of freshly distilled diethyl phosphite was treated witha solution of 3.5 g of sodium methoxide in 20 ml of absolute ethanol,and 70 g (1 mole) of freshly distilled methyl vinyl ketone was thenadded dropwise thereto. The exothermic reaction caused the temperatureof the mixture to rise to about 70° C. After the whole amount of methylvinyl ketone was dropped in, stirring was continued for 21/2 hours andthe reaction mixture was neutralized with glacial acetic acid. After afirst fraction which consisted largely of diethyl phosphite and methylvinyl ketone, the distillation at 0.01 mm yielded the product with aboiling point of 120°-133° C.

EXAMPLE 11 2-Oxo-2-ethoxy-5-ethyl-5-diethylphosphono-1,2-oxaphospholane

138 g (1 mole) of freshly distilled diethyl phosphite was treated with asolution of 1.75 g (0.075 mole) of sodium in 10 ml of absolute ethanol,and 42 g (0.5 mole) of ethyl vinyl ketone was then added dropwisethereto. The exothermic reaction caused the temperature of the mixtureto rise to 70° C. After the whole amount of ethyl vinyl ketone wasdropped in, the reaction was brought to completion by adding another 1 g(0.04 mole) of sodium in 10 ml of absolute alcohol with a rise intemperature to 60° C. observed. Stirring was continued for 2 hours andthe reaction mixture was then neutralized with glacial acetic acid.After a first fraction which consisted largely of diethyl phosphite andethyl vinyl ketone, the distillation at 0.1 mm yielded the producthaving a boiling point of 132°-138° C.

EXAMPLE 122-Oxo-2-ethoxy-3-phenyl-5-methyl-5-diethylphosphono-1,2-oxaphospholane

276 g (2 moles) of freshly distilled diethyl phosphite was treated witha solution of 3.5 g (0.15 mole) of sodium in 20 ml of absolute ethanol.At 40° C., 146 g (1 mole) of benzalacetone was dissolved in 50 ml ofabsolute ethanol, and this solution was added dropwise to the firstsolution. The exothermic reaction caused the temperature of the mixtureto rise to 90° C. over the course of 1 hour. After completion of theaddition of benzalacetone solution, the reaction mixture was stirred for3 hours and neutralized with glacial acetic acid. The product wasisolated in the subsequent distillation at 187°-210° C./0.01 mm.

EXAMPLE 132-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane

10 ml of a mixture of 70.8 g of4-methyl-4-(diethylphosphono)-pentan-2-one (prepared from mesityl oxideand diethyl phosphite) and 82.8 g of diethyl phosphite were dissolved in100 ml of toluene, and the solution was heated to 80° C. A catalyticamount of sodium was added and a vigorous exothermic reaction commenced.The reaction temperature was held between 80° C. and 90° C. byalternately adding the previously prepared mixture and small pieces ofsodium. Altogether 1.65 g of sodium was used as catalyst. The reactiontook 20 minutes. The reaction mixture was subsequently stirred at80°-90° C. for 30 minutes with heating, then cooled and neutralized with4.5 g of glacial acetic acid. This reaction mixture was distilled toyield2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholanewith a boiling point of 156°-161° C./1.1 mm. This substance is identicalto the oxaphospholane manufactured according to Example 4.

EXAMPLE 142-Oxo-2-ethoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane

By carrying out the same procedure as described in Example 13,2-oxo-2-ethoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholanewith a boiling point of 146°-148° C./0.5 mm was obtained from 70.8 g of4-methyl-4-(diethylphosphono)-pentan-2-one and 66.0 g of dimethylphosphite with 1.65 g of sodium as catalyst.

EXAMPLE 152-Oxo-2-ethoxy-3,3,5-trimethyl-5-diisopropylphosphono-1,2-oxaphospholane

By carrying out the same procedure as described in Example 13,2-oxo-2-ethoxy-3,3,5-trimethyl-5-diisopropylphosphono-1,2-oxaphospholanewith a boiling point of 180°-185° C./2 mm was obtained from 70.8 g of4-methyl-4-(diethylphosphono)-pentan-2-one and 99.6 g of diisopropylphosphite with 4.6 g of sodium as catalyst.

EXAMPLE 162-Oxo-2-methoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane

By carrying out the same procedure as described in Example 13,2-oxo-2-methoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholanewith a boiling point of 144°-146° C./0.6 mm was obtained from 83.2 g of4-methyl-4-(dimethylphosphono)-pentan-2-one and 110.4 g of diethylphosphite with 1.15 g of sodium as catalyst. The P³¹ spectrum showed forthe phosphorus atom in the ring a shift of -48 ppm compared with H₃ PO₄as standard.

EXAMPLE 172-Oxo-2-ethoxy-3,3,5-trimethyl-5-diisooctylphosphono-1,2-oxaphospholane

By carrying out the same procedure as described in Example 13,2-oxo-2-ethoxy-3,3,5-trimethyl-5-diisooctylphosphono-1,2-oxaphospholanewas obtained as a viscous, colorless oil from 47.2 g of4-methyl-4-(diethylphosphono)-pentan-2-one and 84.6 g of diisooctylphosphite with 1.15 g of sodium as catalyst. The P³¹ spectrum of thisoil showed for the phosphorus atom in the ring a shift of -49 ppmcompared with H₃ PO₄ as standard.

EXAMPLE 182-Oxo-2-ethoxy-3,3,5-trimethyl-5-di-n-octylphosphono-1,2-oxaphospholane

By carrying out the same procedure as described in Example 13,2-oxo-2-ethoxy-3,3,5-trimethyl-5-di-n-octylphosphono-1,2-oxaphospholanewas obtained as a viscous, pale yellow oil from 47.2 g of4-methyl-4-(diethylphosphono)-pentan-2-one and 84.6 g of di-n-octylphosphite with 1.15 g of sodium as catalyst. The P³¹ spectrum of thisoil showed for the phosphorus atom in the ring a shift of -49 ppmcompared with H₃ PO₄.

EXAMPLE 192-Oxo-2-ethoxy-3,3,5-trimethyl-5-bis-(2-chloroethyl)phosphono-1,2-oxaphospholane

By carrying out the same procedure as described in Example 13,2-oxo-2-ethoxy-3,3,5-trimethyl-5-bis-(2-chloroethyl)phosphono-1,2-oxaphospholanewas obtained from 47.2 g of 4-methyl-4-(diethylphosphono)-pentan-2-oneand 45.2 g of bis-(2-chloroethyl) phosphite. In the P³¹ spectrum, thiscompound showed for the phosphorus atom in the ring a shift of -50.2 ppmcompared with H₃ PO₄ as standard.

EXAMPLE 202-Oxo-2-propyloxy-3,3,5-trimethyl-5-dipropylphosphono-1,2-oxaphospholane

11.8 g of mesityl oxide and 9.8 g of dipropyl phosphite were heated in40 ml of benzene to 80° C. At this temperature, 0.1 g of sodium wasadded, whereupon an exothermic reaction commenced. The reactiontemperature was held at 80°-90° C. without external heating byalternately adding 40.0 g of dipropyl phosphite and 0.4 g of sodium.After all the sodium was added, stirring was continued for 30 minutes.The reaction mixture was then cooled and neutralized with 1.4 g ofglacial acetic acid. The reaction mixture was concentrated in a rotaryevaporator and then distilled in a high vacuum to yield2-oxo-2-ethoxy-3,3,5-trimethyl-5-dipropylphosphono-1,2-oxophospholane inthe form of a colorless oil with a boiling point of 153°-154° C./0.1 mm.The P³¹ spectrum showed for the phosphorus atom in the ring a shift of-67.2 ppm compared with triphenyl phosphate as standard.

EXAMPLE 212-Oxo-2-(2-methoxyethoxy)-3,3,5-trimethyl-5-bis-(2-methoxyethyl)-phosphono-1,2-oxaphospholane

15.7 g of mesityl oxide and 9.2 g of bis-(2-methoxyethyl)phosphite wereheated to 80° C. in 50 ml of benzene. At this temperature, 0.1 g ofsodium was added whereupon an exothermic reaction commenced. Thereaction temperature was held between 80°-90° C. without externalheating by alternately adding 70.0 g of bis-(2-methoxyethyl) phosphiteand 0.6 g of sodium. After all the sodium was added, the reactionmixture was stirred for 30 minutes at 80° C., cooled and neutralizedwith 1.75 g of glacial acetic acid. The reaction mixture wasconcentrated in a rotary evaporator, and the residue was then distilledin a high vacuum to yield2-oxo-2-(2-methoxyethoxy)-3,3,5-trimethyl-5-bis-(2-methoxyethyl)phosphono-1,2-oxaphospholanein the form of a colorless oil with a boiling point of 193°-196° C./0.07mm. The P³¹ spectrum showed for the phosphorus atom in the ring a shiftof -67.2 ppm compared with triphenyl phosphate as standard.

EXAMPLE 222-Oxo-2-allyloxy-3,3,5-trimethyl-5-diallylphosphono-1,2-oxaphospholane

11.5 g of mesityl oxide and 7.4 g of diallyl phosphite were heated to80° C. in 40 ml of benzene. At this temperature, 0.1 g of sodium wasadded. An exothermic reaction started and the reaction temperature washeld at 80°-90° C. without external heating by alternately adding 40.0 gof diallyl phosphite and 0.4 g of sodium. After all the sodium wasadded, the reaction mixture was stirred for 30 minutes at 80° C., thencooled and neutralized with 1.3 g of glacial acetic acid. The reactionmixture was concentrated in a rotary evaporator to yield as residue2-oxo-2-allyloxy-3,3,5-trimethyl-5-diallylphosphono-1,2-oxaphospholanein the form of a pale yellow oil. The P³¹ spectrum showed for thephoshorus atom in the ring a shift of -68.5 ppm compared with triphenylphosphate as standard.

EXAMPLE 232-Oxo-2-ethoxy-3-(4-methoxyphenyl)-5-methyl-5-diethylphosphono-1,2-oxaphospholane

A mixture was prepared of 69.0 g of diethyl phosphite and 5 g of 17%sodium ethoxide solution in ethanol. To this reaction mixture was addedin small amounts 44 g of p-methoxy-benzalacetone, whereupon thetemperature rose from 25° to 89° C. The reaction mixture was stirred for50 minutes and then a further 2.5 g of the 17% sodium ethoxide solutionwas added. After an additional 30 minutes, 3.5 g of diethyl phosphiteand 2.5 g of sodium ethoxide solution were added to give a pale yellow,clear solution which was concentrated in a rotary evaporator. The P³¹spectrum for the phosphorus atom in the ring showed a shift of -58 ppmcompared with triphenyl phosphate.

EXAMPLE 242-Oxo-2-ethoxy-3-(4-methylphenyl)-5-methyl-5-diethylphosphono-1,2-oxaphospholane

By carrying out the same procedure as described in Example 23,2-oxo-2-ethoxy-3-(4-methylphenyl)-5-methyl-5-diethylphosphono-1,2-oxaphospholanewas obtained from 30.2 g of 4-methyl-benzalacetone and 54.7 g of diethylphosphite with 7.8 g of a 17% sodium ethoxide solution in ethanol. TheP³¹ spectrum of the product showed a shift of -58 ppm for the phosphorusatom in the ring.

EXAMPLE 252-Oxo-2-ethoxy-3-(4-chlorophenyl)-5-methyl-5-diethylphosphono-1,2-oxaphospholane

By carrying out the same procedure described in Example 23,2-oxo-2-ethoxy-3-(4-chlorophenyl)-4-methyl-5-diethylphosphono-1,2-oxaphospholanewas obtained from 45.2 g of 4-chloro-benzalacetone and 72.5 g of diethylphosphate with 10 g of a 17% sodium ethoxide solution in ethanol. TheP³¹ spectrum of the product showed a shift of -57.5 ppm for thephosphorus atom in the ring compared with triphenyl phosphate.

EXAMPLE 262-Oxo-2-ethoxy-3-furyl-5-methyl-5-diethylphosphono-1,2-oxaphospholane

By otherwise carrying out the same procedure as described in Example 23,2-oxo-2-ethoxy-3-furyl-5-methyl-5-diethylphosphono-1,2-oxaphospholanewas obtained from 34.0 g of furfurylidene acetone and 72.5 g of diethylphosphite with 10 g of a 17% sodium ethoxide solution in ethanol. TheP³¹ spectrum of the product showed a shift of -55.3 ppm for thephosphorus atom in the ring compared with triphenyl phosphate.

EXAMPLE 27 Flameproofing of polyethylene terephthalate

15 parts of a commercially available polyethylene terephthalate weredissolved in 85 parts of hexafluoroisopropanol. This solution was mixedwith the corresponding amount of flameproofing agent and stirred untilit was homogeneous. Using a film drawing rod, half of the solution wasapplied to a glass plate to a thickness of 0.5 mm. A glass cloth wasthen pressed on the film and was coated by the second half of thesolution in a thickness of 1 mm. Drying in vacuo of 120° C. over 16hours was subsequently carried out. The dried film was drawn from theglass plate and the flammability was determined by the LOI methoddescribed by C. P. Fenimore and J. F. Martin in "Combustions and Flame"10, No. 2, 135-139 (June 1966). In this test, a film is ignited in anatmosphere of nitrogen and oxygen of different volume composition andthe volume ratio is ascertained at which it is still just possible tomaintain combustion of the test specimens. The LOI value is the minimumoxygen concentration in a nitrogen-oxygen mixtue at which the specimenjust still burns. The higher the LOI value of the lower the flammabilityof the sheeting, i.e., the more effective is the addition of theflameproofing agent.

    ______________________________________                                        Flameproofing Agent                                                                        Amount of Flameproofing Agent*                                                                    LOI                                          ______________________________________                                        Flameproofing agent                                                                         5%                 0,225                                        according to                                                                  Example 1                                                                     Flameproofing agent                                                                        10%                 0,250                                        according to                                                                  Example 1                                                                     Without flameproof-                                                                        --                  0,200                                        ing agent                                                                     ______________________________________                                         *Based on polyethylene terephthalate                                     

EXAMPLE 28 Flameproofing of a polyamide

15 parts of a commercially available nylon 6 were dissolved in 85 partsof trifluoroethanol. This solution was mixed with the correspondingamount of flameproofing agent and stirred until homogeneous. Films wereprepared in a manner analogous to that described in Example 27 forpolyethylene terephthalate and LOI values were determined. The followingTable shows how the LOI value increased by addition of the flameproofingagents according to the invention as compared with nylon 6 withoutflameproofing agent.

    ______________________________________                                        Flameproofing Agent                                                                        Amount of Flameproofing Agent*                                                                    LOI                                          ______________________________________                                        Flameproofing agent                                                                         5%                 0,216                                        according to                                                                  Example 1                                                                     Flameproofing agent                                                                        10%                 0,231                                        according to                                                                  Example 1                                                                     Without flameproof-                                                                        --                  0,196                                        ing agent                                                                     ______________________________________                                         *Based on nylon 6?                                                       

EXAMPLE 29 Flameproofing of polyacrylonitrile

201 parts of commercially available polyacrylonitrile were dissolved in80 parts of dimethylformamide. This solution was mixed with thecorresponding amount of flameproofing agent and stirred to homogeneity.Films were prepared in a manner analogous to that described in Example27 for polyethylene terephthalate and the LOI values were determined.The following Table shows how the LOI value increased by addition of theflameproofing agents according to the invention as compared withpolyacrylonitrile without flameproofing agent.

    ______________________________________                                        Flameproofing Agent                                                                        Amount of Flameproofing Agent                                                                     LOI                                          ______________________________________                                        Flameproofing agent                                                                         5%                 0,207                                        according to                                                                  Example 1                                                                     Flameproofing agent                                                                        10%                 0.224                                        according to                                                                  Example 1                                                                     Without flameproof-                                                                        --                  0,189                                        ing agent                                                                     ______________________________________                                    

EXAMPLE 30 Flameproofing of a polyurethane foam

A soft polyurethane foam was manufactured by mixing the followingmaterials:

100 g of a polyhydroxy compound on a polyether basis with a molecularweight of about 3,000 and an OH number of 56

1 g of a siloxane-oxyalkylene copolymer

0.1 g of tin (II) octoate

3.5 g of water

48.2 g of toluene diisocyanate (80:20 mixture of 2,4- and 2,5-isomers)

x g of2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphone-1,2-oxaphospholane(compound of Example 1).

The foam so manufactured was tested for its flammability by the ASTM D1692 test method. For this purpose, test specimens each measuring 150 ×50 × 13 mm were fixed with the 50 × 13 mm surface in the horizontalposition. Marks were made at 25 and 100 mm. The bottom end of thespecimen was then ignited with a gas burner. The ignition time was 60seconds. The foam was termed flameproof if the burned zone was notlonger than 25 mm. If the specimen burned beyond the 25 mm mark and theburned zone was smaller than 125 mm, then the foam was termedself-extinguishing. The length of the burned zone was indicated in mm.If the specimen burned beyond the 125 mm mark, the foam was termedcombustible.

    ______________________________________                                        Amount of x g of flameproof-                                                  ing agent/100 g of polyol                                                                       None     6 g      4 g                                       ______________________________________                                        a) Foaming behavior                                                           creaming time in seconds                                                                        10        13       12                                       rise time in seconds                                                                            90       105      128                                       time in minutes until foam                                                      is no longer tacky                                                                            10        3        2                                        b) Flammability (ASTM D 1692)                                                 burned in mm      150      45       55                                        rate of combustion in                                                           mm/sec.         1.8      1.0      1.5                                       ______________________________________                                    

Individual foam specimens were also subjected to the flameproofing testafter an ageing at 140° C. dry and 90° C. humid over the course of 1, 2,4 and 7 days.

    ______________________________________                                                    Burned Zone in mm                                                                           Burned zone in mm                                               with 6 g of flame-                                                                          with 4 g of flame-                                  Storage conditions                                                                        proofing agent/                                                                             proofing agent/                                     140° dry                                                                           100 g of polyol                                                                             100 g of polyol                                     ______________________________________                                        After 1 day     85                60                                          After 2 days    120               60                                          After 4 days    35                50                                          After 7 days    60                50                                          Storage condi-                                                                tions 90° C humid                                                      After 1 day     40                45                                          After 2 days    60                50                                          After 4 days    60                45                                          After 7 days    65                45                                          ______________________________________                                    

These figures show that a storage resistant flameproofing was obtainedwith 2-oxo-3,3,5-trimethyl-5-diethylphosphone-1,2-oxaphospholane even ifonly 4 g of this compound per 100 g of polyol was used.

What is claimed is:
 1. A compound of the formula Ia ##STR7## whereineach of R_(a), R_(b) and R_(c) independently represents alkyl of 1 to 18carbon atoms, haloalkyl with 2 to 18 carbon atoms, alkoxyalkyl havingnot more than 18 carbon atoms, alkenyl with 3 to 18 carbon atoms,cycloalkyl with 5 to 8 carbon atoms, aralkyl with 7 to 15 carbon atomsaralkyl with altogether 7 to 15 carbon atoms which is substituted byhalogen or alkoxy groups of 1 to 4 carbon atoms,R_(d) representshydrogen or methyl, R_(e) represents hydrogen, alkyl with 1 to 8 carbonatoms, aryl with 6 to 10 carbon atoms or aryl with 6 to 10 carbon atomswhich is susbstituted by halogen, alkyl or alkoxy groups with 1 to 4carbon atoms, and with the proviso that when R_(e) is hydrogen or alkyl,none of R_(a), R_(b) or R_(c) can be alkyl, R_(f) represents hydrogen,methyl or phenyl, and R_(g) represents alkyl with 1 to 8 carbon atoms,aryl with 6 to 10 carbon atoms or aryl with 6 to 10 carbon atoms whichis substituted by halogen, alkyl or alkoxy with 1 to 8 carbon atoms. 2.A compound according to claim 1 wherein each of R_(a) and R_(b)independently denotes alkyl of 1 to 18 carbon atoms, haloalkyl of 2 to18 carbon atoms, alkoxyalkyl having not more than 18 carbon atoms,alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms,aralkyl with 7 to 15 carbon atoms or aralkyl with altogether 7 to 15carbon atoms which is substituted by halogen or alkoxy groups of 1 to 4carbon atoms,R_(c) is the same as either R_(a) or R_(b), R_(d)represents hydrogen or methyl, R_(e) represents hydrogen, alkyl with 1to 8 carbon atoms, aryl with 6 to 10 carbon atoms or aryl with 6 to 10carbon atoms which is substituted by halogen, alkyl or alkoxy of 1 to 4carbon atoms, and with the proviso that when R_(e) is hydrogen or alkyl,none of R_(a), R_(b) or R_(c) can be alkyl, R_(f) represents hydrogen,methyl or phenyl, and R_(g) represents alkyl with 1 to 8 carbon atoms,aryl with 6 to 10 carbon atoms or aryl with 6 to 10 carbon atoms whichis substituted by halogen, alkyl or alkoxy with 1 to 8 carbon atoms. 3.A compound according to claim 1 wherein R_(a), R_(b) and R_(c) areidentical and represent alkyl of 1 to 8 carbon atoms, alkoxyalkyl with 3to 6 carbon atoms, 2-chloroethyl, 2-bromoethyl, alkenyl with 3 to 4carbon atoms, cyclohexyl or benzyl; R_(d) represents hydrogen or methyl;R_(e) represents hydrogen, methyl, ethyl, phenyl, naphthyl, phenyl ornaphthyl substituted by 1 to 5 chlorine or bromine atoms, p-tolyl,p-anisyl or xylyl, and with the proviso that when R_(e) is hydrogen,methyl or ethyl, R_(a), R_(b) and R_(c) cannot be alkyl; R_(f)represents hydrogen or methyl; and R_(g) represents methyl, ethyl,phenyl, phenyl substituted with 1 to 5 chlorine or bromine atoms,p-tolyl, xylyl or p-anisyl.
 4. The compound of claim 1 which is2-oxo-2-cyclohexyloxy-3,3,5-trimethyl-5-dicyclohexylphosphono-1,2-oxaphospholane.5. The compound of claim 1 which is2-oxo-2-ethoxy-3-phenyl-5-methyl-5-diethylphosphono-1,2-oxaphospholane.6. The compound of claim 1 which is2-oxo-2-(2-methoxyethoxy)-3,3,5-trimethyl-5-bis(2-methoxyethyl)phosphono-1,2-oxaphospholane.7. The compound of claim 1 which is2-oxo-2-allyloxy-3,3,5-trimethyl-5-diallylphosphono-1,2-oxaphospholane.8. The compound of claim 1 which is2-oxo-2-ethoxy-3-(4-methoxyphenyl)-5-methyl-5-diethylphosphono-1,2-oxaphospholane.9. The compound of claim 1 which is2-oxo-2-ethoxy-3-(4-methylphenyl)-5-methyl-5-diethylphosphono-1,2-oxaphospholane.10. The compound of claim 1 which is2-oxo-2-ethoxy-3-(4-chlorophenyl)-5-methyl-5-diethylphosphono-1,2-oxaphospholane.